Over the past decade, electrospraying has proven to be a promising method for the preparation of amorphous solid dispersions, an established formulation strategy to improve the oral bioavailability of poorly soluble drug compounds. Due to the lack of fundamental knowledge concerning adequate single nozzle electrospraying conditions, a trial-and-error approach is currently the only option. The objective of this paper is to study/investigate the influence of the different formulation and process parameters, as well as their interplay, on the formation of a stable cone-jet mode as a prerequisite for a reproducible production of monodisperse micro- and nanoparticles. To this purpose, different polymers commonly used in the formulation of solid dispersions were electrosprayed to map out the workable parameter ranges of the process. The experiments evaluate the importance of the experimental parameters as flow rate, electric potential difference and the distance between the tip of the nozzle and collector. Based on this, the type of solvent and the concentration of the polymer solutions, along with their viscosity and conductivity, were identified as determinative formulation parameters. This information is of utmost importance to rationally design further electrospraying methods for the preparation of amorphous solid dispersions.